Crystal and molecular structure of 3-(2-amino-pyridinium)-propionate monohydrate

Article abstract of DOI:10.1016/j.molstruc.2005.10.016

A novel betaine derivative, 3-(2-amino-pyridinium)-propionate monohydrate, has been synthesized and its structure studied by X-ray diffraction, FTIR, Raman, ¹H and ¹³C NMR spectroscopies and by DFT calculations. The crystals are monoclinic, space group P2₁/c with a=8.0800(16), b=15.242(3), c=7.1698(14) ?, β=104.30(3)° and Z=4. Each oxygen atom of the carboxylate group is engaged in two intermolecular hydrogen bonds, one with water molecule and the other with amine group. The water molecules link the molecules of 3-(2-amino-pyridinium)-propionate into planar zigzag chains along the b axis. The screening constants for ¹H and ¹³C atoms have been calculated by GIAO/B3LYP/6-31 G(d,p) and analyzed. Linear correlations between the experimental ¹H and ¹³C chemical shifts and the computed screening constants have been obtained. Raman and FTIR spectra of the title betaine have been investigated.

Full text of DOI:10.1016/j.molstruc.2005.10.016

Journal of Molecular Structure 786 (2006) 25–32
www.elsevier.com/locate/molstruc
Crystal and molecular structure of 3-(2-amino-pyridinium)-
propionate monohydrate
*
Mirosław Szafran , Iwona Kowalczyk, Andrzej Katrusiak
´
Faculty of Chemistry, Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznan, Poland
Received 29 July 2005; received in revised form 4 October 2005; accepted 8 October 2005
Available online 28 November 2005
Abstract
A novel betaine derivative, 3-(2-amino-pyridinium)-propionate monohydrate, has been synthesized and its structure studied by X-ray
diffraction, FTIR, Raman, 1H and 13C NMR spectroscopies and by DFT calculations. The crystals are monoclinic, space group P21/c with aZ
˚
8.0800(16), bZ15.242(3), cZ7.1698(14) A, bZ104.30(3)8 and ZZ4. Each oxygen atom of the carboxylate group is engaged in two
intermolecular hydrogen bonds, one with water molecule and the other with amine group. The water molecules link the molecules of 3-(2-amino-
1
pyridinium)-propionate into planar zigzag chains along the b axis. The screening constants for H and 13C atoms have been calculated by
GIAO/B3LYP/6-31 G(d,p) and analyzed. Linear correlations between the experimental 1H and 13C chemical shifts and the computed screening
constants have been obtained. Raman and FTIR spectra of the title betaine have been investigated.
q 2005 Elsevier B.V. All rights reserved.
Keywords: 3-(2-amino-pyridinium)-propionate; X-ray diffraction, Hydrogen bonds; FTIR; Raman; 1H and 13C NMR spectra; B3LYP calculation
1. Introduction
which the carboxylate group in pyridine betaines is replaced by
azolyl or benzoimidazoyl-2 [2].
In zwitterionic molecules, R3XC–ðCH2Þn–YOKð2–4Þ, oppo-
sitely charged quaternary ammonium (XZN), quaternary
phosphonium (XZP) or tertiary sulfonium (XZS) groups are
connected with the necked carboxylate group (YZCOO) via
methylene groups (nZ1–10). The above compounds are known
as betaines (R3NC–(CH2)n–COOK), phosphonium betaines
(R3PC–(CH2)n–COOK), or sulfonium betaines (R2SC–
(CH2)n–COOK) [1]. When the carboxylate group is replaced
by sulfato or sulfito groups than sulfobetaines (R3NC–(CH2)n–
SO2OK), sulfitobetaines ðR3NC–ðCH2Þn–OSOK2 Þ, sulfatobe-
taines ðR3NC–ðCH2Þn–OSOK3 Þ, and phosphinatebetaines
(R3PC–(CH2)n–SO2OK) are formed [1]. Replacement of the
carboxy or sulfonic groups by a phospinate or phosphonate
group led to phosphinatebetaines (R3NC–(CH2)n–PaO
(R)OK), phosphonatebetaine (R3NC–(CH2)n–PaO(OR)OK),
phosphitobetaines (R3NC–(CH2)n–O–PaO(H)OK), and phos-
phatobetaines (R3NC–(CH2)n–OPaO(OH)OK) [1]. Another
group of betaines is heterocyclic betaines and their salts, in
Relatively large group are pyridine betaines which are good
proton acceptors. Structures of several pyridine betaines and
their 1:1 and 2:1 complexes with HCl, HBr, HClO4, H2SO4,
HSO3F, C6H5–CH2–COOH, C6Cl5OH and 2,6-Cl2K4-NO2–
C6H2–OH have been determined by X-ray diffraction [3–25].
An interesting examples of betaines are pyridinium betaines
of squaric acid, in which one oxygen atom of dianion of squaric
acid is replaced by R-pyridinium ring [26,27].
In previous studies we have analyzed conformation of
2-aminopyridinium-acetate (2-aminopyridinium betaine;
IUPAC name, 1-carboxymethyl-2-amino-pyridinium inner
salt) and its monohydrate, 2-NH2–C5H4NCCH2–COOK$H2O
[28]. In this work, we report synthesis, crystal structure, FTIR
and Raman spectra and some DFT results of 3-(2-amino-
pyridinium)propionate monohydrate (monohydrate of 1-car-
boxyethyl-2-amino-pyridinium inner salt), 2-NH2–
C5H4NCCH2–CH2–COOK$H2O.
2. Experimental
*
Corresponding author. Tel.: C48 61 8291320; fax: C48 61 8658008.
E-mail address: szafran@amu.edu.pl (M. Szafran).
2.1. Synthesis
2-NH2-pyridine (0.1 m) and 3-bromo-propionic acid
(0.1 m) were stirred for 30 h at room temperature up
0022-2860/$ - see front matter q 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2005.10.016

26
M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
Table 2
to solidification and then left to stand for 2 days. The crude 3-
(2-amino-pyridinium)propionic acid bromide was recrystal-
lized from acetonitrile, m.p. 250–252 8C, yield 84%.
3-(2-Amino-pyridinium)propionic acid bromide (1 eqiv)
was dissolved in water and propylene oxide (1.3 eqiv)
dissolved in methanol was added slowly. After 4 days the
reaction mixture was extracted with ether and the residue was
evaporated under reduced pressure to dryness. The raw 3-(2-
amino-pyridinium)-propionate monohydrate, 2-NH2PB2$H2O
was recrystallized from methanol, m.p. 124–126 8C, yield
63%.
2
˚
Atomic coordinates and equivalent isotropic displacement parameters (A ) for
3-(2-amino-pyridinium)-propionate monohydrate
x
Y
z
U (eq)
N(1)
0.8148(2)
0.7079(2)
0.5469(2)
0.7765(3)
0.9414(3)
1.0473(3)
0.9812(3)
0.7588(3)
0.7113(3)
0.6542(2)
0.6314(2)
0.62942(19)
0.2381(2)
0.298(4)
0.291(4)
0.5043
0.16828(9)
0.2403(2)
0.1972(3)
0.1041(3)
0.2568(3)
0.3497(3)
0.3930(3)
0.3379(3)
0.1840(3)
0.3457(3)
0.2971(3)
0.12739(19)
0.4334(2)
0.1966(3)
0.324(4)
0.123(4)
0.0408
0.0285(4)
0.0265(4)
0.0377(5)
0.0313(4)
0.0379(5)
0.0414(5)
0.0366(5)
0.0352(5)
0.0373(5)
0.0305(4)
0.0396(4)
0.0403(4)
0.0499(5)
0.060
C(2)
0.23829(11)
0.22916(11)
0.32212(12)
0.33151(13)
0.25813(15)
0.17841(14)
0.07767(12)
0.03003(13)
N(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
Deuterated compound was obtained by dissolving the
sample in D2O (twice), evaporating to dryness and recrystalli-
zation from a CH3OD.
C(9)
K0.06467(12)
K0.08960(10)
K0.10904(9)
0.03831(12)
0.0541(19)
0.047(2)
0.1839
O(1)
O(2)
O(1w)
H(1w)
H(2w)
H(21)
H(22)
H(3)
0.060
2.2. Instrumentation
0.046(7)
0.067(10)
0.057(8)
0.044(6)
0.054(7)
0.052(7)
0.059(8)
0.051(7)
0.045
0.4981
0.2679
0.1031
The X-ray diffraction measurements were carried out using
a KUMA KM-4 CCD diffractometer. The structure was solved
by direct methods with SHELXS-97 [29] and refined by the
full-matrix least squares method on F2 data using SHELXL-97
[30]. The crystal data and details concerning the data collection
and structure refinement are given in Table 1. Atomic
coordinates and equivalent displacement parameters are listed
in Table 2. The parameters in the CIF form are available as
Electronic Supplementary Information from Cambridge
0.7063
0.3713
0.2314
H(4)
0.9853
0.3871
0.3854
H(5)
1.162(4)
1.0507
0.2616(19)
0.1291
0.449(4)
0.3672
H(6)
H(71)
H(72)
H(81)
H(82)
0.8502
0.0464
0.1468
0.6611
0.0793
0.0736
0.6197
0.0617
0.3815
0.8089
0.0299
0.4563
0.045
U(eq) is defined as one third of the trace of the ortogonalized Uij tensor.
Crystallographic Data-base Centre (CCDC reference number
283154).
Table 1
Crystal data and structure refinement for 3-(2-amino-pyridinium)-propionate
monohydrate
The calculations were performed using the Gaussian 98
package [31] at the B3LYP [32,33] levels of theory with the
6-31G(d,p) basis set [34].
Empirical formula
Formula weight
Temperature (K)
C8H10N2O2
166.18
NMR spectra were measured with a Varian Gemini 300 VT
spectrometer, operating at 300.07 and 75.4614 MHz for 1H and
13C, respectively. Typical conditions for the proton spectra
were pulse width 328, acquisition time 5 s, FT size 32 K and
digital resolution 0.3 Hz per point, and for the carbon spectra
pulse width 608, FT size 60 K and digital resolution 0.6 Hz per
point; the number of scans varied from 1200 to 10,000 per
spectrum. 13C and 1H chemical shifts, measured in D2O
293(2) K
0.71073
Monoclinic
P21/c
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
˚
a (A)
8.0800(16)
˚
b (A)
15.242(3)
˚
c A)
7.1698(14)
b (deg)
104.30(3)
3
˚
Volume (A )
855.7(3)
Z
4
Calculated density (g/cm3)
Absorption coefficient (mmK1
F(000)
1.290
)
0.095
352
Crystal size (mm)
0.5!0.3!0.2
3.22–29.41
q range for data collection (deg)
Index range
K10%h%10
K20%k%20
K5%l%9
Reflections collected/unique
R(int)
6219/2172
0.0355
Completeness to qmax
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [IO2s(I)]
R indices (all data)
qZ29.90, 90.9%
Full-matrix least squares on F2
2172/0/135
1.262
R1Z0.0354, wR2Z0.1000
R1Z0.0538, wR2Z0.1229
0.287 and K0.277
K3
˚
Largest diff. peak and hole (e A
Fig. 1. ORTEP drawing (at 50% probability level) of 3-(2-amino-pyridinium)-
propionate monohydrate with atom numbering.
)

M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
27
Fig. 2. Auto-stereogram of two neighboring hydrogen bonded chains of 3-(2-amino-pyridinium)-propionate monohydrate and water molecules. Hydrogen bonds are
denoted by the dashed lines.
relative to internal dioxane, were 67.35 and 3.55 ppm,
respectively. The FTIR spectra in Nujol and Fluorolube
emulsions were measured at 2 cmK1 resolution using a Bruker
IFS 113v spectrometer, which was evacuated to avoid water
and CO2 absorption. Raman spectrum was recorded on a
Magna 760 Nicolet operating at the 1064 nm exciting line of a
Nd:YAG laser.
data indicate that in both 2-amino-pyridine betaines the NH2
group appears between amino and imino tautomers
(C–NH25CaNH).
3.2. FTIR and Raman spectra
The FTIR and Raman spectra of the investigated betaine are
shown in Fig. 4. The intense broad absorption in the 3500–
2600 cmK1 region corresponds to the overlapping nOH and
nNH vibrations of water molecule and NH2 group. On
deuteration this absorption shifts to lower wavenumbers and
3. Results and discussion
3.1. Molecular parameters
Molecular structure of 3-(2-amino-pyridinium)-propionate
monohydrate and the numbering scheme are shown in
Figs. 1–3, respectively. The functional atomic coordinates
with equivalent thermal parameters, bond lengths and bond
angles are listed in Tables 2 and 3, respectively. Each water
molecule links two adjacent betaine molecules via two slightly
˚
different hydrogen bonds of lengths 2.818 and 2.886 A into a
planar zigzag chains along b axis (Figs. 2 and 3). The NH2
group is engaged in two hydrogen bonds of the lengths 2.859
˚
and 2.828 A with the COO groups of neighboring betaines. The
angle between the planes through the pyridine ring and COO
group is 76.27(9)8. In 2-aminopyridine acetate the hydrogen
bonds between the NH2 and COOK groups are slightly longer
(Table 4). As shown in Table 3 the C–O bond lengths in the
betaine investigated are similar, while in 2-aminopyridine
acetate these bonds lengths are much different [24].
The bond length between NH2 and the pyridine ring is equal
˚
1.315(3) A. Slightly longer distances are in 2-aminopyridine
˚
acetate monohydrate (1.329(2) A) [24] and its hydrochloride
˚
(1.330(3) A) [25]. These values are close to the average of
˚
single C–N (1.46 A) and double CaN (1.15 A) bonds. In
˚
˚
2-amino-4-methyl-pyridine the C–NH2 distance is 1.363 A
˚
[35] and becomes shorter (1.329 A) on protonation [36]. These
Fig. 3. Auto-stereogram of the crystal packing of 3-(2-amino-pyridinium)-
propionate monohydrate. Hydrogen bonds are denoted by the dashed lines.

28
M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
Table 3
˚
X-Ray and calculated bond lengths (A) and bond angles (deg) for 3-(2-amino-pyridinium)-propionate monohydrate
˚
Bond length (A)
Bond angle (8)
Torsion angle (8)
N(1)–C(2)
N(1)–C(6)
N(1)–C(7)
N(2)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(7)–C(8)
C(8)–C(9)
C(9)–O(1)
C(9)–O(2)
1.360(2)
1.362(2)
1.478(2)
1.315(3)
1.416(2)
1.342(3)
1.396(3)
1.347(3)
1.496(3)
1.529(3)
1.244(2)
1.245(2)
N(1)–C(2)–C(3)
N(1)–C(6)–C(5)
N(1)–C(7)–C(8)
N(2)–C(2)–N(1)
N(2)–C(2)–C(3)
C(2)–N(1)–C(6)
C(2)–N(1)–C(7)
C(7)–N(1)–C(6)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(7)–C(8)–C(9)
O(1)–C(9)–O(2)
O(1)–C(9)–C(8)
O(2)–C(9)–C(8)
117.42(17)
121.51(19)
111.20(16)
121.71(16)
120.87(17)
121.24(16)
122.46(16)
116.30(16)
120.83(18)
120.26(18)
118.7(2)
C(6)–N(1)–C(2)–N(2)
C(7)–N(1)–C(2)–N(2)
C(6)–N(1)–C(2)–C(3)
C(7)–N(1)–C(2)–C(3)
N(2)–C(2)–C(3)–C(4)
N(1)–C(2)–C(3)–C(4)
C(2)–C(3)–C(4)–C(5)
C(3)–C(4)–C(5)–C(6)
C(4)–C(5)–C(6)–N(1)
C(2)–N(1)–C(6)–C(5)
C(7)–N(1)–C(6)–C(5)
C(2)–N(1)–C(7)–C(8)
C(6)–N(1)–C(7)–C(8)
N(1)–C(7)–C(8)–C(9)
C(7)–C(8)–C(9)–O(1)
C(7)–C(8)–C(9)–O(2)
K179.56(17)
0.8(3)
0.3(3)
K179.35(16)
K179.16(17)
1.0(3)
K1.5(3)
0.7(3)
0.6(3)
K1.1(3)
178.59(19)
K96.8(2)
83.5(2)
113.72(16)
126.03(18)
118.34(17)
115.58(16)
K179.28(16)
K8.9(3)
173.40(18)
Table 4
Geometry of hydrogen bonds in 3-(2-amino-pyridinium)-propionate and 2-amino-pyridinium-acetate monohydrates
D–H/A
D/A
D–H
H/A
!DHA
Symmetry code
nND
nOD
2-NH2C5H4NCCH2CH2COOK$H2O
N(2)–H(21)/O(1)
N(2)–H(22)/O(2)
O(1w)–H(1w)/O(2)
2.859(2)
2.828(2)
2.818(2)
2.886(2)
0.85
0.71
0.95
0.77
2.02
2.13
1.89
2.14
170.3(3)
171.1(3)
164.3(3)
163.0(3)
1Kx, Ky, Kz
1Kx, K0.5Cy, 0.5Kz
x, y, z
2405
2223
2467
2603
O(1w)–H(2w)/O(1)
x, y, 1Kz
2-NH2C5H4NCCH2COOK$H2O [24]
N(2)–H(21)/O(1)
2.967
2.866
2.795
2.828
0.999
0.850
0.861
0.788
1.976
0.850
0.861
0.788
171.3
168.4
176.2
172.4
0.5Kx, K0.5Cy, z
Kx, 1Ky, Kz
x, y, z
2482
2397
N(2)–H(22)/O(2)
O(1w)–H(1w)/O(1)
O(1w)–H(2w)/O(1w)
2413
2585
K0.5Cx, y, 0.5Kz
5.0
4.0
3.0
2.0
1.0
0.0
(a)
(b)
1.2
0.9
0.6
0.3
0.0
3000
2000
1500
1000
500
Wavenumbers/cm-1
Fig. 4. Spectra of 3-(2-amino-pyridinium)-propionate monohydrate: (a) Raman spectrum in the solid state; and (b) FTIR spectrum in Nujol and Fluorolube
emulsions; dotted line denotes spectrum of deuterated molecule (2-ND2–C5H4NC–CH2CH2COOK$D2O).

M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
29
The nas(COOK) and ns(COOK) are located at 1648 and
1386 cmK1 and are at slightly higher wavenumbers than in
pyridine betaine [40] and betaines [39–42]. The band at
1684 cmK1, which shifts on deuteration to 1319 cmK1
corresponds to bNH2 vibration. In 2-aminopyridine this band
is at 1650 cmK1 in liquid but at 1635 cmK1 in vapour [40]. The
bNH2 band is at 1169 cmK1 and on deuteration it is shifted to
895 cmK1. Probable assignments of the bands observed are
listed in Table 5.
Table 5
Tentative assignments of the observed absorption bands in the Raman and
FTIR spectra of 3-(2-amino-pyridinium)-propionate monohydrate, and its
deuterate analogue
2-NH2PB2$H2O
Assignment
2-ND2PB2$D2O
Assignment
Raman
IR
IR
3500–2600
nH2OCnNH2 2603
nD2O
nD2O
nND2
nND2
nCH
2437
2405
2223
3106
3088
3019
2964
2916
1694
1643
1584
1523
nCH
3105
3067
3028
2988
2918
1319
1652
1582
1526
1477
1454
1423
1403
1382
1318
1267
nCH
nCH
1
3.3. H and 13C NMR
nCH
nCH
nCH2
nCH2
nCH2
dND2
nasCOO
n-Ring
n-Ring
n-Ring
bCH2
n-Ring
n-Ring
nsCOO
bCH
The proton chemical shift assignments (Table 6) are based
on the 2D COSY experiments, in which the proton–proton
connectivity is observed through the off-diagonal peaks in the
counter plot. The 2D heteronuclear shifts correlated counter
map (HETCOR) has been used to identify resonances in the
13C NMR spectra.
nCH2
1684
1648
1590
1524
1470
1458
1424
1402
1386
dNH2
nasCOO
n-Ring
n-Ring
n-Ring
bCH2
n-Ring
n-Ring
nsCOO
1457
1419
1401
1348
1332
1275
1228
1210
1167
1135
1085
1063
1046
1021
930
The relations between the experimental 1H and 13C
chemical shifts (dexp) and the GIAO (gauge including
atomic orbitals) screening tensors (scalc), which are now
widely used in efficient implementation [43–45], are
usually linear and described by the following equation:
1263
bCH
bCH
bCH
1
dexpZaCb*scalc. The differences in H and 13C chemical
1194
1169
1138
1083
bCH
1196
895
bCH
bNH2
bCH
bND2
bCH
shits between unsubstituted pyridine betaines [46] and their
2NH2-derivatives (Ref. [26] and Table 6) follow the
additive rules for NH2 substituent [37].
1154
1116
1052
1027
1013
929
bCH
bCH
bCH
bCH
1044
1024
931
867
803
772
687
610
552
507
485
426
bCH
bCH
bCH
bCH
3.4. B3LYP calculations
gCH
nCC
871
gCH
862
gCH
gCH
gCH
gODO
b-Ring
g-Ring
797
gCH
801
Seven isolated entities, denoted as 2–8, were optimized at
the B3LYP/6-31G(d,p) level of theory and their structures are
shown in Fig. 5. These structures differ in the type of hydrogen
bonds. In all optimized structures one proton of the amine
group is transferred to the carboxylate group and the
intramolecular HN$$$HO hydrogen bond of lengths between
751
gCH
767
682
gOHO
g-Ring
g-Ring
g-Ring
g-Ring
g-Ring
512
611
609
551
537
486
431
456
425
g-Ring
g-Ring
Table 6
The abbreviations are: n, stretching; b, in-plane-bending; g, out-of-plane-
Chemical shifts (d, ppm) in D2O and calculated GIAO nuclear magnetic
shielding tensors (scal) for 3-(2-amino-pyridinium)-propionate monohydrate
bending modes.
dexp
dpred
scalc
57.64
D
four bands at 2603, 2467, 2405 and 2223 cmK1 are
distinguished. The first two bands belong to D2O molecule,
but the last two to the ND2 group.
C(6)
C(5)
C(4)
C(3)
C(2)
C(7)
C(8)
H(6)
H(5)
H(4)
H(3)
H(7)
H(8)
143.4
115.9
140.4
114.5
154.7
51.9
143.6
105.6
139.5
122.0
163.4
52.9
9.2
91.90
61.29
77.09
39.82
139.50
154.06
24.71
26.00
24.98
25.73
27.92
29.35
K14.4
5.4
In the betaine investigated the NH2 groups are engaged in
shorter hydrogen bonds but water molecule in longer ones in
comparison to those in 2-amino-pyridinium acetate monohy-
drate (Table 4). The differences between nND and nOD bands
in the two betaines agree well with the differences in their
hydrogen bonds.
K13.0
K2.1
35.8
36.8
7.65
7.91
K1.09
K1.19
K0.74
K1.05
6.69
7.60
6.83
4.18
2.54
6.73
7.60
6.42
4.23
2.61
An interesting point is the difference between the nasNH2
and nsNH2 vibrations in amines. A typical difference between
these frequencies is DnZ65–130 cmK1 [37–39]. The larger
difference (DnZ182 cmK1) in the betaine investigated agrees
well with the presence of two different hydrogen bonds
(Table 4).
The predicted GIAO chemical shifts were computed from the linear equation
dexpZaCbscalc with a and b determined from the fit of the experimental data.
D (ppm) is effect of NH2 on chemical shifts on betaine. aCZ207.4382;
bCZK1.1076; r2Z0.9831, aHZ36.1495; bHZK1.1432; r2Z0.9933.

30
M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
Fig. 5. Comparison of the X-ray (1) and B3LYP/6-31G(d,p) (2–8) most stable structures: 2-NH2–C5H4NC–CH2CH2COOK$H2O (1–6), 2-NH2–C5H4NC
CH2CH2COOK$H2O$H2O (7) and 2-NH2–C5H4NC–CH2CH2COOK (8).
–
Table 7
Selected X-ray and DFT parameters of 3-(2-amino-pyridinium)-propionate monohydrate, 2-NH2–C5H4NCCH2–CH2–COOK$H2O
X-Ray
B3LYP/6-31G(d,p)
1
2
3
4
5
6
7a
8
E (Hartree)
Erel (kcal/mol)
m (Debye)
N(2)–C(2)
N(2)–H
K647.281384 K647.274953 K647.279402 K647.276627 K647.285245 K723.715330 K570.844616
0
2.42
6.46
3.67
5.41
7.935
1.305
1.017
6.891
1.302
1.021
7.608
1.306
1.017
7.407
1.300
1.017
7.741
1.305
1.018
7.695
1.314
1.017
8.217
1.304
1.017
1.315
0.851,
0.709
!C(2)–N(2)–H
N(2)/O(1)
!N(2) /H–O(1)
O(2)–C(9)–O(1)
O(2)–C(9)–O(1)–H
HOH/O(1)
!HOH/O(1)
HOH/O(2)
!HOH/O(2)
H–N(2)/HOH
!H–N(2)/HOH
O(1)/OH2
25.2, 113.3
110.9
2.652
176.8
121.7
174.8
2.828
110.1
2.666
176.9
122.9
176.0
110.6
2.644
177.2
122.2
K176.5
2.944
130.2
3.139
124.2
114.4
2.580
174.1
123.1
175.7
2.953
144.5
109.4
110.3
2.652
176.9
121.3
176.6
3.032
124.9
2.841
160.5
3.091
149.8
110.7
2.700
176.1
122.8
176.0
126.0
122.2
177.2
2.818
164.3
2.886
162.9
2.828
161.5
2.731
177.4
2.657
179.5
1.335
1.212
4.463
4.618
4.097
2.731
3.977
O(1)H)/OH2
C(10)–O(1)
1.244
1.245
4.208
4.801
4.387
5.112
1.322
1.222
3.792
4.799
5.532
6.337
5.115
1.333
1.213
3.807
4.793
5.117
3.125
4.211
175.4
126.2
K52.9
127.4
K178.5
1.6
1.335
1.215
3.812
4.753
4.586
4.375
4.508
1.336
1.212
3.775
4.801
5.268
3.041
4.221
1.330
1.334
1.212
3.826
4.796
C(10)–O(2)
1.220
N(1)/O(1)
N(1)/O(2)
N(1)/OH2
N(2)/OH2
Av. N(1,2)/O(1,2)OH2 4.627
!N(2)H/OH2
N(1)–C(7)–C(8)–C(9)
C(7)–C(8)–C(9)–O(1)
C(7)–C(8)–C(9)–O(2)
N(2)–C(2)–N(1)–C(6)
N(2)–C(2)–N(1)–C(7)
O(1)–C(9)–O(2)/HOH
O(2)–C(9)–O(1)/HOH
3.782
4.789
3.963/5.526
3.091
K179.3
123.8
K49.7
130.7
K178.3
1.5
126.7
K60.9
117.4
K178.3
2.7
122.0
K176.8
K74.3
103.3
122.6
K52.5
128.0
K179.1
0.3
127.7
K53.5
126.7
K178.4
1.7
K8.9
173.4
K179.6
0.8
K44.8
132.2
K179.7
K0.4
K178.0
0.8
178.3
72.9
180.0
K93.7
93.3
81.4
a
Dihydrate, 2-NH2–C5H4NCCH2–CH2–COOK$2H2O.

M. Szafran et al. / Journal of Molecular Structure 786 (2006) 25–32
31
Table 8
Conformations of the NCCH2CH2COO(H) moiety in betaines and complexes determined by X-ray diffraction
Compound
u(1)
u(2)
u(3)
u(4)
N
C/O(1)
N
C/O(2)
Ref.
2-NH2–C5H4NCCH2CH2COOKH2O
2-Br–C5H4NCCH2CH2COOH$Br
(C5H5NCCH2CH2COO)2H$Br
K179.3(2)
179.9(6)
K63.0
K8.9(3)
170.3(6)
166.1
173.4(2)
K11.8(11)
K13.9
K16.1
1.0
4.208
4.761
3.045
4.108
4.280
4.302
3.193
4.791(4)
4.828(4)
4.493
4.363
4.858
4.647
4.191
4.801
4.273
4.202
3.279
3.076
3.017
3.757
4.224(4)
4.213(4)
3.312
3.210
4.216
4.351
4.900
2.5
[19]
[15]
K2.8
0.3
9.7
6.2
2.4
47
K74.4
165.4
ðC5H5NCCH2CH2COOHÞ2SO42K
68.0(3)
K66.3(3)
63.1
179.8(3)
K175.8(3)
K97.1
172.7(3)
179.5(3)
K175.2(3)
K179.5(5)
173.6
[17]
4.0
C5H5NCCH2CMe2COOH$Cl
80.4
[19]
[20]
[20]
[47]
[47]
[47]
2-(HOCH2)–C5H4NCCH2CH2COOH$Br
2-(HOCH2CH2)–C5H4NCCH2CH2COOH$Br
[(C5H5NCCH2CH2COO)2$Ag2]n(ClO4)2n
[(C5H5NCCH2CH2COO)2$Ag2(NO3)2]n
[(Me3NCCH2CH2COO)2Ag2$H2O][ClO4]2
K159.3(3)
179.5(2)
78.9(4)
77.6(6)
K169.9
170.8
K6.6(5)
K1.6(5)
8.3(4)
3.6(7)
K6.9
7
60.1
K120.1
180.0
Me3NCCH2CH2COOH$H2O$Br
180.0
K0.0
K0.0
[48]
Torsion angles: u(1)ZNC–C(7)–C(8)–C(9); u(2)ZC(7)–C(8)–C(9)–O(1); u(3)ZC(7)–C(8)–C(9)–O(2); u(4)ZO(2)–C(9)–O(1)–H.
˚
2.580–2.700 A is present in 2–5 and 7–8 (Table 7). Differences
between 1 and 2–8 occurr also in the N(1)–C(7)–C(8)–C(9) and
C(7)–C(8)–C(9)–O(1/2) dihedral angles. In 2–5 and 7–8 the
conformation of N(1)–C(7)–C(8)–C(9) units is anticlinal. In
crystals, as the data in Table 8 show, the conformation of N(1)–
C(7)–C(8)–C(9) units in some betaines is antiperiplanar (trans)
but synclinal (gauche) in others. In 6 the water molecule is
engaged in two hydrogen bonds, one as a proton acceptor with
The FTIR spectrum of the investigated betaine has
been analyzed and found in good agreement with the
crystal structure. Good correlations between the exper-
imental 13C and 1H chemical shifts in D2O solution of
3-(2-amino-pyridinium)-propionate and GIAO/B3LYP/6-
31G(d,p) calculated isotropic shielding tensors (dexp
aCb*scalc) have been obtained.
Z
˚
the COOH group (OaC–O–H$$$OH2, 2.657 A) and the other
as a proton donor with the NH group (H–O–H$$$N–H,
Acknowledgements
˚
2.731 A). Conformer 6 has the lowest energy, which is
´
DFT calculations were performed at the Poznan Super-
computing and Networking Centre.
probably caused by electrostatic interactions between the
positively charged NC(1) and NC(2) with oxygens of COOK
group and water molecule; the average distance of these
˚
attractive interactions is the shortest in 6 and equal 3.977 A
(Table 7).
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